Lithium aluminium hydride (LiAlH4) is a strong reducing agent which dissolves well in polar solvents such as diethyl ether (Et2O) or tetrahydrofuran (THF). In the solid, powdered state it is difficult to handle on account of its high reactivity towards air and water, as well as the risk of dust explosions. On an industrial scale, therefore, LiAlH4 solutions in organic solvents are preferably used. LiAlH4 can be prepared by reacting an aluminium halide, in particular aluminium chloride (AlCl3), with lithium hydride (LiH) in an ethereal solvent. In the synthesis developed by Schlesinger et al. (J. Amer. Chem. Soc. 69, 1199 (1947)), Et2O is employed as the solvent:

LiAlH4 is very readily soluble in Et2O with a proportion of 28%, but this solvent requires complex safety measures owing to its low flash point and boiling point. It is therefore avoided as far as possible in industrial applications.
Commercially supplied LiAlH4 solutions generally contain no Et2O but are supplied as a 10% solution in THF or a 15% solution in THF/toluene (Chemetall brochure “Industrial Use”). THF has a significantly higher boiling point than Et2O. Thus, the boiling point of THF is 66° C. but that of Et2O is only 35° C.
There are various methods of preparing solutions of LiAlH4 in THF or solvent mixtures containing THF. One possibility consists in the reaction of sodium aluminium hydride with lithium chloride (LiCl) (WO-A-97/06097):

Disadvantages of this process are the relatively long reaction times and poor yields.
On an industrial scale, THF solutions of LiAlH4 are prepared by dissolving solid, solvent-free LiAlH4 in THF or THF/co-solvent. In this case, the solid LiAlH4 is first synthesised as a solution in diethyl ether, which is subsequently evaporated completely at elevated temperatures and under reduced pressure. However, this process also has serious disadvantages. Firstly, it is relatively expensive owing to its complexity.
Furthermore, the thermal loading of the LiAlH4 during evaporation leads to partial decomposition as in diagram 3:

Li3AlH6 is insoluble and therefore cannot be used for reduction processes. The solutions prepared by dissolving solid LiAlH4 are markedly cloudy owing to the content of elemental aluminium and Li3AlH6; the solids content must be removed, e.g. by filtration or decantation. This is because residual contents of elemental aluminium not only impair the handling properties but also cause a clear deterioration in the storage stability, since they catalytically accelerate the decomposition process according to diagram 3.
In order to achieve a solution of LiAlH4 in THF, the synthesis according to diagram 1 can also, in principle, be carried out directly in THF. However, this has the disadvantage that, on the one hand, the solubility of the AlCl3 employed is only relatively low. Thus, at room temperature (RT), the solubility of AlCl3 in THF is only 16%, whereas in Et2O it is 57%. On the other hand, the LiCl formed as a by-product is readily soluble in THF. Thus, the solubility of LiCl in THF is 4.8%, but in Et2O it is <0.001%. In this way, only dilute solutions of LiAlH4 in THF could be prepared, and these are at the same time contaminated with LiCl.